Method of preparing a phenolic aldehyde resin and resin composition for an adhesive system to be applied to glass fibers

ABSTRACT

A method of preparing a thermoplastic, long-chain water-soluble, phenolic formaldehyde resin and the composition are provided to enhance the flexibility and resistance to compression fatigue breakage of glass fibers to which the resin has been applied. The method involves two steps. In the first step, the phenolic compound and the formaldehyde are reacted to less than 100 percent completion in an amount so that the formaldehyde to resorcinol ratio is in the range of about 0.6 to about 2.0 and at an acidic pH and for a period of time equivalent to about 1 hour to about 20 hours when the temperature is in the range of about 30° F.(-31 1.1° C.) to about 122° F. (50° C.) to produce a resinous mixture having a predominant amount of trimer polymer along with minor amounts of dimer and higher oligomer polymers and along with unreacted phenolic compound and aldehyde. In the second stage the pH of the reaction is adjusted within the range above of about 7.0 to about 7.5 and the reaction is continued between the unreacted phenolic compound and aldehyde and resinous mixture to produce a resinous mixture composition that is thermoplastic, and water soluble and has a predominant amount of trimer polymer with slight cross-linkage and a minor amount of dimer and higher oligomer polymers. 
     The composition of the phenolic aldehyde resin prepared according to this method is a mixture of polymer forms, containing predominantly the trimer polymer.

BACKGROUND OF THE INVENTION

This invention is related to a method for preparing phenolic aldehyde resin. More particularly, this invention relates to a method for preparing resorcinol-formaldehyde resin for use in an adhesive system for the adhesion of glass fiber to rubber to produce reinforced rubber goods.

Filamentary materials have been used extensively as reinforcing material in rubber to produce reinforced rubber products, such as pneumatic tires, power-drive belts, conveyor belts, high pressure hoses and the like. The filamentary materials that are used to reinforce rubber material include naturally occuring or synthetic filaments and may be in the form of individual fibers, groups of fibers in the form of strand, rope, cord, roving fabric and the like. The naturally occuring fibers include cotton, silk, ramie and the synthetic fibers include, rayon, nylon, polyester and glass fibers.

Glass fibers are excellent filamentary material for reinforced rubber and are superior to the natural and synthetic organic filamentary materials, since the glass fibers do not become elongated or deformed under stress to the extent of the other filamentary materials. Unlike other filamentary materials, particular combinations of glass fibers with encapsulating coating cooperate to yield reinforced rubber materials that have greater strength than even the glass or the coating material alone. While filamentary materials, other than glass fibers, which are subject to substantial stress elongation, are essentially limited in tensile strength to the basic strength of their fibers, even if coated properly, coated glass fibers have greater strength than the glass alone. For example, the low modulus of elasticity of glass may be exploited to provide reinforced rubber tires having superior road performance, if an appropriate coating medium is provided to transfer stresses to all fibers in the glass fiber cord so that loading throughout is substantially uniform. This phenomenon is illustrated by the observation that a typical uncoated fiber glass cord (G75,5/0, filament count 2,000 i.e., 2,000 filaments of G fiber of about 9.14 micro meter diameter, 15,120 meters per kilogram, 5 strands per cord) has a tensile strength of about 35 to 40 pounds (156 to 178 newtons) ASTM test G178-52, but when coated with a coating, e.g. resorcinol formaldehyde latex coating, such a cord has a tensile strength of about 50 to about 70 pounds (220 to 311 newtons).

The above-mentioned coated glass fiber cord, GT-75,5/0 has found particular utility in the reinforcement of rubber for use in power transmission belts and fiber glass reinforced tires and the like. In such a coated glass fiber cord, a resorcinol formaldehyde latex coating is used as the adhesive system to transfer the stresses and to provide adhesion between the glass fibers and the rubber. Typically, the resorcinol formaldehyde, phenol aldehyde resin, useful in adhesive systems for the adhesion of glass fibers to rubber is produced by a method using a basic pH environment, i.e. around a pH of 8 to 10. The phenolic aldehyde resin usually has an aldehyde level to phenolic compound level, usually resorcinol, of 0.4 to 0.8 to one phenolic compound on a mole basis. Such a resin is characterized by a low degree of polymerization and minimum molecular weight. A particularly useful phenol aldehyde condensate, which is a resorcinol formaldehyde resin, has a ratio of 0.6 formaldehyde to 1 resorcinol, and is sold under the designation Penacolite® R-2200 resin.

There are several methods known in the art for preparing phenol aldehyde polymers to be used in adhesive systems. As early as 1947 in U.S. Pat. No. 2,385,372 (Rhodes) a permanently fusible resin was prepared from dihydroxybenzene (resorcinol) and an aldehyde in two stages so that a catalyst was not present during the early stages of a reaction. It was theorized that having the catalyst present in the early stages of the reaction would cause a resin to be too thick for the removal of the water produced by the reaction. The problem was overcome by employing a two stage reaction, wherein the dihydroxybenzene (resorcinol) is reacted with the aldehyde without a catalyst until a major portion of the reaction is completed. Then either an alkaline or acid catalyst is added and the last increment of aldehyde reacts with the dihydroxybenzene.

Also a several stage reaction has been employed to produce a phenolic aldehyde condensate in U.S. Pat. No. 4,025,454 (Rouzier), wherein a pre-condensate of formaldehyde, resorcinol and a para-substituted phenol and a pre-condensate of resorcinol and formaldehyde are used. In a first stage, resorcinol and a para-substituted phenol with two active methylene groups are condensed in the presence of an acid catalyst. In the second stage formaldehyde is condensed with the product of the first stage in an alkaline medium. Then in the third stage the product of the second stage is dissolved in water along with a resorcinol pre-condensate to form the phenoplastic system, which is a mixture of phenol aldehyde condensates, then combined with an elastomeric latex to form the adhesive for textile fibers.

Also, in U.S. Pat. No. 3,956,205 (Higginbottom) a resole is produced by a two-stage reaction. The first stage of the reaction is carried out under novolac forming conditions, where an acid catalyst is used to give a pK that is less than 5. In the first stage, one mole of phenol is reacted with 0.05 to 0.30 moles of formaldehyde in order to favor the formation of the dimer polymer and suppress the formation of higher oligomers. In the second stage the reaction is conducted in the presence of a basic catalyst, which has a pK greater than 9 with the addition of 1.75 to 3.5 moles of formaldehyde per mole of original phenol for the resole reaction. At the end of the reaction, the catalyst is neutralized by addition of acid to reduce the pH to between 6 and 8.5 to produce the resole resin.

The phenolic aldehyde resins of the prior art, such as Penacolite® resorcinol formaldehyde resin, and those produced by the aforementioned multi-stage processes can be improved upon for use in an adhesive system to coat glass fibers that are used to reinforce rubber products. An improvement of the phenolic aldehyde resin is desired to give the coated glass fibers more flexibility and better resistance to compression fatigue breakage to yield more durable and longer lasting reinforced rubber products.

One of the many reinforced rubber products that would benefit from the use of coated glass fibers having more flexibility and better resistance to compression fatigue are pneumatic tires. A bias belted tire having coated glass fibers that have more flexibility and better resistance to compression fatigue would have improved wear characteristics and would give extended mileage. Also radial tires having glass fiber belts, alone or in combination with other filamentary material belts, containing coated glass fibers having more flexibility and better resistance to compression fatigue would give extended mileage and improved handling.

It is an object of the present invention to provide a method for preparing a thermoplastic, long-chain, phenolic formaldehyde resin having improved flexibility and having toughness and which is comprised of a substantial amount of the trimer polymer and to provide the said resin composition for use in an adhesive system used in coating glass fibers to render the glass fibers more flexible and more resistant to compression fatigue breakage.

SUMMARY OF THE INVENTION

According to the present invention a thermoplastic, long-chain, phenolic aldehyde resin, which has a substantial amount of trimer polymer, is prepared. The method involves a two-step reaction. In the first step a phenolic compound and the aldehyde are reacted in amounts so that the phenolic compound to aldehyde ratio is in the range of about 0.6 to about 2 and to less than 100 percent completion in an acid medium for a period of time equivalent to about 1 hour to about 20 hours at a temperature in the range of about 30° F. (-1.1° C.) to about 122° F. (50° C.) to produce a phenolic aldehyde resinous mixture having a substantial amount of trimer polymer and a smaller amount of dimer or higher oligomer polymers than trimer along with unreacted phenolic compound and unreacted aldehyde. In the second step the pH of the resinous mixture from the first stage is adjusted within in the range of above 7 to about 7.5 to continue the condensation reaction of the phenolic compound and aldehyde and resinous mixture to produce the more flexible and tough, thermoplastic, long-chain, water soluble, phenolic aldehyde resin containing predominantly the trimer polymer.

The resinous mixture produced is a thermoplastic, water soluble, long-chain, phenolic aldehyde resin that is idealy suited for use in an adhesive system to coat glass fibers to give the coated glass fibers better adhesion to rubber stock to produce reinforced rubber products.

Generally the phenolic compound and aldehyde undergoing reaction and any acid or basic catalyst, if any, used to control the pH in the respective steps of the process of the invention can be any phenolic compound, aldehyde, acid or basic catalyst known to those skilled in the art of phenolic aldehyde resins. The term "resin" refers to synthetic resins that are organic substances of high molecular weight synthesized from relatively simple chemical compounds by condensation polymerization reactions.

The phenolic aldehyde resin produced by the carefully controlled two step process of the present invention gives phenolic aldehyde resins that are flexible and tough and that when used in an adhesive system for coating glass fibers render the coated glass fibers more flexible and more resistant to compression fatigue. Because of the pH control in both steps of a two step process, and because the reactants added to the first step are not completely reacted in the first step, and because of the relation of the temperature and time conditions in both steps, the trimer polymer is the predominant polymer formed by the two step reaction. Other polymer forms such as the dimer and higher oligomer polymer forms are also produced but to a much smaller amount than the trimer. The trimer polymer form can be represented by the following formula: ##STR1## where R is hydrogen or a hydroxyl group or mixture thereof, the trimer may also have one or more pendant methyol groups from the phenolic rings in the trimer.

The phenolic aldehyde resin prepared according to the above described process is actually a mixture of polymer forms where the trimer form is the predominant polymer form. This phenolic aldehyde resin is an excellent resin for use in an adhesive system for bonding glass fibers to rubber stock. The resin is first combined with a conventional elastomeric latex so that the resin is present in an amount of about 5 to about 50 parts by weight of the resin per 100 parts by weight of elastomeric latex solids. Other components such as wax, antioxidants and bond enhancers, one example is resorcinol, cross-linking retarding agents, for example concentrated ammonia can be added to the adhesive system. Sufficient water is present or added to adjust the total solids content of the adhesive system from about 20 to about 40 percent solids. This adhesive system is used to coat glass fiber materials such as individual glass fibers and groups of glass fibers in the form of strand, rope, cord, roving, fabric and the like.

DETAILED DESCRIPTION

The phenolic aldehyde resin of the present invention has, as mentioned above, a critical composition, i.e. predominantly trimer polymers in the mixture of polymers that constitute the phenolic aldehyde resin, and is prepared by a carefully controlled, critical multi-step process. In the first step the reactants are reacted to less than 100 percent completion in an acid pH of around 3 to 5.5 and in the second step the resinous reaction is continued at a pH in the range of about 7 to about 7.5.

It is believed, but the invention is not limited by this belief that the critical process results in the critical composition in the following manner. The phenolic compound has a strong ortho-para-directing influence because of the hydroxyl group. If resorcinol is the phenolic compound, then the compound is doubly activated in the 2, 4 and 6 position on the ring. When the phenolic compound to aldehyde ratio is around one, a resin is obtained in an acid medium that is permanently fusible and soluble. Very little, if any cross-linking occurs, and the resin consists predominantly of chains in which the phenol nuclei are connected by means of methylene bridges to the activated positions of the phenolic nuclei. In the acid medium the 2 and 6 positions of the phenolic nuclei are favored for the condensation reaction. The rate of reaction for the formation of the resin is directly proportional to the hydrogen-ion concentration. By controlling the acidic pH in the first step to be acidic, and by controlling the temperature and residence time within the specified ranges, the resin reaction is less than 100 percent complete. The result is that along with the resin produced in the first step there is also present some unreacted aldehyde and possibly some unreacted phenolic compound. Since the resin formation reaction of the first step is less then 100 percent complete, even though the ratio of phenolic compound to aldehyde may be less than 1, about 0.6 to 1, the resin produced is still permanently fusible and soluble. The mean molecular weight of the resin from the first step of the reaction is generally less than 1,000. The resinous product from the first step contains a predominant amount of the trimer polymer; it is actually a resinous mixture that also contains a minor amount of dimer polymer and a minor amount of higher oligomer polymers such as tetramers and pentamers. It is desirable to keep the amount of higher oligomers to a minimum, since these higher oligomers are not water soluble. The resin mixture chain with a substantial amount of trimer polymer has good flexibility which is transferable to a substrate coated with the phenolic aldehyde resin of the present invention.

The reaction mixture from the first step has its pH adjusted to a range of above 7 to about 7.5. Although the rate of resin formation in the presence of basic catalysts is independent of the hydroxyl ion concentration above low concentrations of the catalyst, the small amount of basic catalyst added to bring the pH to above 7 to 7.5 is low enough so that the hydroxyl ion concentration has an effect on the rate of reaction. The resinous material from the first step continues to react with the unreacted aldehyde and any unreacted phenolic compound present from the first step to form methylol groups which condense further upon aging of the resinous material in the second step to produce a long-chain, slightly cross-linked but still essentially linear, thermoplastic, phenolic resin having a preponderance of trimer polymers in the mixture of polymers that compose the phenolic aldehyde resin. Since a basic pH is used only in the second step, the formation of the phenolic alcohols in the second step is mostly limited to methylol rather than dialcohols or trialcohols, and this limiting effect promotes the growth of the essentially linear, long chain, thermoplastic resin of the first step. The limitation of the methylol phenolic alcohols along with the directing influence of a basic environment, to reaction at the 2, 4 and 6 positions, leads to the growth of cross-links in the essentially linear chain in the resinous mixture of the first step. The addition of the methylol groups to provide a slight amount of cross-linking in the linear chain of the resinous material from the first step gives the resinous material a degree of toughness, while still maintaining the flexibility of the linear chain. The reaction in the second step is continued for about 1 to about 5 hours to obtain the long chain resin having good flexibility with a small amount of cross-linking to give the resin a degree of toughness. The branching is not to such an extent that the resin becomes cross-linked and infusible.

In the process and composition of the present invention, the structure of the phenolic compound is an important factor in the characteristics of flexibility and toughness of the resin and substrates the resin coats. The rate of resinification depends on the nature and extent of the substitution of the phenolic compound. With the phenolic compound reacting with the aldehyde in the ortho- and para-positions to one or more hydroxyl groups on the ring, there should be at least two open positions either ortho or para to a hydroxyl group. The phenolic compounds useful in the process and composition of the present invention include phenol, resorcinol and mixtures thereof as well as these compounds in admixture with small amounts of cresol and mixtures of its isomers, xylenol or mixtures of its isomers, a mixture of homologues of phenol and dihydric phenols, such as phloroglucinol, orcinol, cresorcinol and m-xylorcinol. It is preferred to use resorcinol as the phenolic compound and in the alternative a mixture of resorcinol and phenol.

The aldehyde that is useful in the process and composition of the present invention is one that acts as a methylene donor and is soluble in the raction medium. Aldehydes that can be used include: formaldehyde, commonly used as 37 percent aqueous solution referred to as formalin, various polymers of formaldehyde, such as paraformaldehyde, hexamethylene-tetramine, acetaldehyde and furfural, and mixtures thereof. It is preferred to use formaldehyde in the form of formalin.

Hereinafter in the specification, the phenolic compound will be referred to as the preferred phenolic compound, resorcinol, and the aldehyde will be referred to as the preferred aldehyde, formaldehyde. But it is to be understood that any of the aforementioned phenolic compounds or aldehydes can be used, as described, in lieu of or in combination with the resorcinol and formaldehyde.

The amounts of resorcinol and formaldehyde that are used are those that give a mole ratio of resorcinol to formaldehyde in the range of about 0.6 to about 2. The preferred ratio is 1 mole of resorcinol to 1.5 moles of formaldehyde to give a mole ratio of resorcinol to formaldehyde of around 0.65.

If too little an amount of resorcinol or too much formaldehyde are used, an infusible, cross-linked resin will be produced instead of a fusible, thermoplastic resin with very little cross-linking that is flexible and tough. If too much resorcinol and too little an amount of formaldehyde are used the resin produced will not be as flexible as possible because the number of long chain, trimer polymers, in the polymer mixture will not be very large.

In the first step of the present invention the type of acid catalyst that can be used include: sulfuric acid, oxalic acid, hydrochloric acid, sulfamic acid, benzene sulfonic acid toluene sulfonic acid or trifluoroacetic acid. The concentration of acid catalyst can be in the range of around 0.001 to 0.002 mole equivalents per mole of resorcinol but the acid pH of the first step reaction can by any acid pH with sufficient amount of catalyst added to achieve the desired pH. Preferably the pH of the first step reaction is that acid pH achieved by combining the resorcinol and formaldehyde for the reaction. Most preferably this pH that is achieved by combining the reactants autocatalysis is in the range of about 3 to 5.5. An acid pH greater than that achieved by autocatalysis can be used by adding a small amount of basic catalyst. If the pH is above about 5.5, then resorcinolic alcohols like methylol may be produced and cross-linking may occur.

The reaction in the first step is conducted by adding the resorcinol and formaldehyde to a reaction vessel. Preferably, resorcinol and formaldehyde, as formalin are added to a reaction vessel in the proper amounts to give the desired mole ratio. If a monohydric phenol, like phenol, is present to any degree, the reaction conditions must be elevated since monohydric phenols react more slowly than resorcinol or polyhydric phenols. Generally, the temperature for the resin reaction between resorcinol and formaldehyde in the first step is in the range of about 30° F. (-1.1° C.) to about 122° F. (50° C.) when the residence time for the resin reaction in first step is in the range of about 1 hour to about 20 hours. An equivalent residence time and temperature can be used, i.e. if the temperature is increased beyond 122° F. (50° C.), then the residence time can be shortened to less than 4 hours. Also if the temperature is decreased below 30° F. (-1.1° C.), then the residence time must be increased beyond 20 hours.

At the end of the reaction in the first step a resinous or polymeric mixture is produced that has a major amount of trimers and a smaller amount of dimers and higher oligomers of the phenolic compound, preferably resorcinol, along with some unreacted formaldehyde and some unreacted resorcinol. The major amount of trimer is at least around 40 percent of the reacted materials in the polymeric mixture.

The resinous mixture of the first step is conducted to a second step where the pH of the resinous mixture is adjusted to be in a range of above 7 to about 7.5. This adjustment is made by adding a basic catalyst to the resinous mixture. Suitable basic catalysts include: sodium hydroxide, potassium hydroxide, and other alkali metal hydroxides as well as alkali metal carbonates, and alkaline earth hydroxides. These can be used as solids but are preferably used in an aqueous solution. The concentration of basic catalyst is generally around 3 percent per mole of resin and preferably about 0.01 to about 0.06 mole of catalyst per mole of resin.

After the pH of the resinous mixture has been adjusted to the proper pH, the resin reaction is continued so the unreacted formaldehyde reacts with the resin and unreacted resorcinol. The reaction is conducted at a temperature in the range of about 50° F. (1.0° C.) to about 140° F. (60° C.) when the residence time is in the range of about 0.75 hours to about 20 hours. If the temperature is increased or decreased above or below this range, the residence time is inversely adjusted and therefore, any temperatures and residence times can be used as long as the solution does not boil or freeze.

If the pH is above about 7.5 then too many methylol groups will form and the resin may become overly cross-linked. If the pH is below about 7.0 then the acid type resin reaction of the first step will continue to occur and the linear trimer polymer chain and smaller amount of other polymer forms will not obtain the small amount of cross-linking to give a tough flexible resin.

The above described two-step process may be conducted in a batch-type reaction in one vessel or in a semi-continuous-type or continuous type reaction in one vessel with several stages or in several vessels where the reactants and products ae cascaded from one vessel to the next. The reaction vessels used in the two-step process are any reaction vessels known to those skilled in the art to be useful for resi forming reactions.

In the preferred embodiment of the present invention resorcinol and formaldehyde in the form of formalin are reacted in a mole ratio in the range of 0.6 to 2.0. The pH of the mixture of resorcinol and formaldehyde at this mole ratio is around 3.5 to 5.5 which is sufficient for the reaction in the first step of the process. Therefore in the preferred embodiment an acid catalyst is not needed to obtain a pH in the range of 3.5 to 5.5 in the reaction between resorcinol and formaldehyde which is in the form of formalin. In an alternative embodiment with different reactants when the pH of the first step reaction is not in the range of less than 5.5 and greater than 3, an acid catalyst must be used. The reaction in the first step between resorcinol and formaldehyde is conducted at a temperature preferably around 20° to around 35° C. for a period of time around 3 to around 10 hours. The resinous product of the first step comprises a major amount of trimer polymer of resorcinol formaldehyde with minor amounts of dimer and higher oligomers of resorcinol and formaldehyde along with unreacted formaldehyde and a smaller amount of unreacted resorcinol. The pH of this resin mixture is adjusted to be in the range of above 7 to about 7.5 by adding about 0.01 to about 0.06 moles an aqueous solution of potassium hydroxide per mole of resin, then the reaction of the resorcinol formaldehyde resin, unreacted resorcinol and unreacted formaldehyde is continued in the second step at pH of above about 7 to about 7.5 at a temperature preferably in the range of around 20° to around 35° C. and for a period of time in the range of around 2.5 hours to around 10 hours. The resinous product issued from the second step is a flexible but tough resorcinol formaldehyde resin which is thermoplastic and being a mixture of polymer forms with a major amount of trimer polymer that contains a small amount of cross-linking.

The resorcinol formaldehyde resin of the invention is combined directly with an aqueous rubber latex to form an adhesive system for binding fiberous materials to rubber. The elastomeric latices useful in the adhesive system are the conventional latices used in the formation of rubber adhesive systems. Suitable elastomeric latices are the synthetic rubber latices such as vinylpyridine-styrene-butadiene copolymer latices sold commercially under the trademark GEN-TAC, GOODRITE, or PYRATEX. Also polybutadiene dispersions, styrene-butadiene latices, reclaimed rubber dispersions, butyl rubber dispersions, annd ethylenepropylene-butadiene terpolymer rubber dispersions can be used. Also other latices that can be used include natural rubber latex which may be the crude rubber latex or rubber latex that contains added material or that has been treated to alter the character of the rubber, for instance by degradation or by oxidation, or both. For instance, it may contain any desired accelerators, vulcanizers, stabilizers, dispersing agents or any other substance, such as, those commonly used in the rubber industry. When rubber is used as an artificial dispersion of either natural or any other known synthetic rubber it may likewise contain additional substances as rubber accelerators, vulcanizers, stabilizers, dispersing agents and the like. The type or kind of rubber dispersion or elastomeric latex to be used depends to some extent upon the type or kind of rubber stock to which it is desired to bond the fiberous material, particularly the glass fibers. Besides the specified elastomeric latices and dispersions any combination of the above is hereby disclosed for the purposes of this invention.

Generally, the adhesive system can be made in any manner known to those skilled in the art. The resin to elastomeric latex ratio of the adhesive system should range between about 5 to about 50 parts by weight of the resin per 100 parts by weight of elastomeric latex solids. The resorcinol formaldehyde resin-elastomeric latex mixture may also contain such additives as a wax to protect the elastomer in the coating composition attack by ultraviolet light; zinc oxide, magnesium oxide, litharge, or red lead can be incorporated to the adhesive system to promote cross-linking or curing of the elastomeric latex and improve resistance of the composition to aging, heat, and light; anti-oxidants to protect the materials from degradation due to oxygen; treated diatomaceous earths or chemical diatomaceous earths and other ingredients known to those skilled in the art may be added to the adhesive system to impart varying characteristics thereto.

The aqueous adhesive system of the present invention should have a pH of between about 7 to about 10. Any pH adjustment may be made by the addition of an aqueous caustic solution, such as, sodium hydroxide or the ammonium hydroxide to arrive at the desired pH. Also caustic solution like sodium hydroxide or ammonium hydroxide can be added to tie up any unreacted formaldehyde, if any, and thereby raise the pH of the adhesive system. However, if the composition added thereto is a vinyl pyridine latex (PH 10.2), the dip may not require further pH adjustment. The adhesive system thus prepared is ready for immediate use, or because of its stability may be held for as long as a one week period before being used to coat filamentary materials, particularly glass fibers. The adhesive system may be applied to the surface of fiberous materials particularly glass fibers by any conventional method such as dipping, spraying or spreading.

The filamentary material to which the adhesive system of the present invention can be applied includes reinforcing materials, such as, natural and synthetic organic fibers like cellulosic fibers, nylon fibers, polyester fibers and glass fibers. Particularly, the filamentary material are glass fibers. Generally in the method of forming glass fiber cord in accordance with the present invention the glass fibers are formed at a fiber-forming bushing, sized with an aqueous sizing composition, which is a conventional glass fiber sizing composition, gathered into strand and wound on a forming package. This process is more fully described in U.S. Pat. Nos. 3,437,517; 3,459,585; and 3,887,389, hereby incorporated by reference. The forming packages are then dryed and mounted on a creel, unwound and coated with the adhesive system coating composition of the present invention.

In the preferred embodiment, the preferred resorcinol formaldehyde resin produced by the aforementioned process is combined with a polybutadiene latex such as LPM-2374L available from Goodyear, SR-272 available from Firestone and GF-8025 available from General. The ratio of resorcinol formaldehyde resin to rubber latex should range between about 5 to about 50 parts resin per 100 parts rubber latex solid, that is, the amount of rubber on a dry basis of the latex. The rubber includes those aforementioned rubbers, such as, polybutadiene, SBR, vinyl pyridine and the like. Less than about 5 parts of resin will provide insufficient adhesion, whereas, greater than about 50 parts of resin for 100 parts latex is economically undesirable. Also to the resin latex adhesive system, there is added an antioxidant of the phenolic type such as Bostex 294 available from Akron Dispersion of Akron, Ohio. The amount of the antioxidant which is added, is usually in the range of around 1 part per 100 parts of dry rubber to enhance the coating flexibility over a wide range of temperatures. Also added is an aliphatic wax, such as, Mobilcer Q wax available from Mobile Company, which is added in an amount in the range of around 5 parts per 100 parts of rubber. Also another antioxidant like Paracure A09 antioxidant is added in an amount of around 0.5 parts per 100 parts of rubber. After the adhesive system coating composition has been prepared a small amount of concentrated ammonia (28% solution) is added to tie up unreacted formaldehyde so that no further resin crosslinking occurs. The amount added is usually less than 1 part per 100 parts rubber. The ammonia addition stabilizes the adhesive system coating composition and prolongs its shelf life. It has also been found that the bonding characteristics of the adhesive system can be improved by adding around 1 part per 100 part of rubber of resorcinol after the addition of the ammonia solution. The added resorcinol increases the adhesion level of the adhesive system by increasing the resin content and increases the polarity of the adhesive system coating composition for better wettability and impregnation.

A preferred method of producing glass fiber bundles coated with the adhesive coating composition of the present invention is to contact a continuous bundle, for example, strand which has been previously sized, with the coating composition of the invention, and dry the coating within the bundle, and then cure the coating residing within and about the bundle to produce a coated cord suitable for rubber reinforcement. A particularly advantageous method for producing the glass fiber bundles of the invention based upon the method described in U.S. Pat. No. 3,619,252 "Manufacture of Elastomeric Coated Glass Fibers" by Alfred M. Roscher, which is hereby incorporated by reference. This invention is particularly applicable to glass fiber, filament bundles, having complete filament encapsulation and having a relatively high ratio of coating weight i.e., about 15-40 percent to glass weight.

A plurality of glass fiber strand, which have been previously sized, are combined in parallel relation and passed between a guide in tangential contact across motor driven rollers. The rollers are partially immersed in the adhesive system coating composition of the present invention and these rollers pick up the coating composition when rotated. The coating which is picked up is brought into contact with the glass fiber strand, coating and impregnating the combined bundle of strand. Relaxation of the tension in the combined bundle of strands opens the spacings between the fibers and between the strands enhancing impregnation of the coating into the bundle. Typically the coating composition solids of the aqueous dip will be about 20-40 percent, depending upon the total amount of coating composition solids to be imparted into the glass fiber cord. Lower solid level will produce cord with low coating add on based on the weight of the glass and a higher solids content will produce a coating glass fiber cord having a high amount of coating composition solids based on the weight of the glass. Thus, coating add on weight is about 15 to about 40 percent based on the weight of the glass fibers, more preferably about 20 to about 30 percent to provide a coated glass fiber bundle or cord which is useful for the reinforcement of elastomeric matrices.

After contacting the fiber glass bundle with the coating composition of the present invention for a sufficient time to fully impregnate the bundle with the water and solids containing dip, the bundle is passed through a dielectric heater or drying oven. The drying oven so designed and operated that water is removed rapidly from the inside of the bundle as well as from the surface of the bundle without substantial migration of the solids from the interior to the surface of the bundle and without excessive blistering.

The dryed glass bundle is then subjected to heat in order to partially cure the rubber adhesive coating throughout the bundle. It is preferred to partially cure the coating while completing the curing of the coating on the glass fiber, when it is embedded in the rubber matrix being reinforced during the curing of the rubber in the final article.

A second method for making the glass fiber bundles of the invention is based upon the method described in U.S. Pat. No. 3,718,448 entitled "Fiber Forming and Coating Process" by Warren W. Drummond and Donald W. Denniston which is assigned to the present assignee and is incorporated herein by reference and made a part hereof.

As to the rubber to which the coated fiber glass cord will adhere, the invention contemplates any compound of natural rubber stock or any compound of synthetic rubber stock, such as, polymerized isoprene, or polymerized butadiene, or polymerized halogen substituted butadiene, such as, a halogen-2-butadiene-1,3-polymer, for example, chloro-2-butadiene-1,3-polymer and other types.

The invention is further illustrated by the following Examples wherein parts are parts by weight unless otherwise indicated. The Examples should be construed to illustrate the invention but not to limit the invention.

EXAMPLE I

The long-chain, thermoplastic resorcinol formaldehyde resin of the present invention is prepared by first adding about 70 to 75 percent of the total water at about 22° to 25° C. to a premixed tank. Resorcinol in an amount of 57.6 pounds (26 kg.) is added to the water in the premix tank and agitated until completely dissolved. Then 61.2 pounds (27.8 kg.) of formaldehyde is added to the premix tank containing the water and resorcinol. The resorcinol and formaldehyde are reacted in the aqueous solution at a temperature of 78°-80° F. (25.6°-26.7° C.) at a pH of 5.0 plus or minus 0.5 for a period of time of four hours. A solution of potassium hydroxide in water was prepared by adding 1.8 pounds (0.82 kg.) of potassium hydroxide to 24 pounds (10.39 kg.) of water and mixing together until the potassium hydroxide is dissolved. At the end of four hours the aqueous solution of potassium hydroxide was slowly added to the premix tank containing the reacted resorcinol and formaldehyde. After the addition the temperature was maintained at 75°-80° F. (24°-27° C.) at a pH of 7.5 and the reaction was continued for a period of time of 5 hours. The resorcinol formaldehyde resin product contained after 5 hours is the long chain, thermoplastic, water soluble, resin of the present invention, having a predominant amount of trimer polymers that are slightly cross-linked with a lesser amount of uncrosslinked trimer polymers and dimer polymers and oligomers that may or may not be slightly cross-linked making up the polymer mixture that constitutes the resin.

EXAMPLE II

Eleven gallons (3.79 L) of deionized water at 110° F. (43.3° C.) was added to a tank and 19.2 pounds (8.71 kg.) of resorcinol was added to the water in the tank and agitated until completely dissolved. To this aqueous mixture resorcinol there was added 20.4 pounds (9.25 kg.) of formaldehyde and the temperature was adjusted to 78°-80° F. (26°-27° C.) at a pH of 5.0 plus or minus 0.5. This temperature was maintained for a period of time of four hours. In the meantime an aqueous solution of potassium hydroxide was prepared by mixing 0.6 pounds (0.27 kg.) potassium hydroxide and 8 pounds (3.63 kg.) of deionized water. At the end of four hours the aqueous solution of potassium hydroxide was added slowly to the resorcinol formaldehyde reaction mixture in the tank. After the addition of the aqueous potassium hydroxide solution the temperature was maintained at 75°-80° F. (24°-27° C.) at a pH of 7.5 for a period of time of 5 hours. After the 5 hours the resorcinol formaldehyde resin product was the long-chain, thermoplastic, water soluble, resorcinol formaldehyde resin of the present invention.

EXAMPLE III

Twelve gallons of deionized water at 110° C. (43.3° C.) was added to a tank and 20.8 pounds (9.4 kg.) of resorcinol was added to the water in the tank and agitated until completely dissolved. To this aqueous solution of resorcinol there was added 22.8 pounds (10.3 kg.) of formaldehyde. The formaldehyde and resorcinol aqueous solution was reacted at a temperature of 78°-80° F. (26°-27° C.) at a pH of 5.0 plus or minus 0.5 for a period of time of four hours. Meanwhile an aqueous solution of potassium hydroxide was prepared by dissolving 0.6 pounds (0.27 kg.) of potassium hydroxide in two gallons of deionized water. At the end of four hours the aqueous solution of potassium hydroxide was slowly added to the resorcinol formaldehyde reaction mixture. After the addition of the aqueous potassium hydroxide the temperature of the reaction mixture was maintained at 75°-80° F. (24°-27° C.) and the pH of the reaction was continued for a period of time of five hours after which the resorcinol formaldehyde product was the long chain thermoplastic, water soluble, resorcinol formaldehyde resin of the present invention.

EXAMPLE IV Production of Adhesive System with Long-Chain, Thermoplastic, Water Soluble Resorcinol Formaldehyde Resin

To a main mix tank there was 1,440 pounds (653 kg.) of polybutadiene latex, Goodyear 2374 and 1,080 pounds (490 kg.) of vinylpyridene and polybutadiene latex, Goodyear 5622. To this mixture of latices there was added 133 gallons (503.5 L) of deionized water and while doing that 21.6 pounds (9.8 kg.) of antioxidant, Boxtex 294 was added with deionized water to the mix tank. To a separate mixing tank there was added 46 gallons of deionized water and 10.8 pounds (4.9 kg.) of the antioxidant Paracure A-09. To this mixture there was added 108 pounds (4.9 kg.) of wax, Mobilcer Q and the solution was mixed for ten minutes and then added to the mixture of polybutadiene and vinylpyridine latices in the main mixing tank. After the resorcinol formaldehyde resin produced according to Example 1 had been aged for 9 hours it was added slowly to the mix tank containing the mixture of polybutadiene and vinylpyridine latices and wax and antioxidant. After the resorcinol formaldehyde resin was added, the mixture was aged for 10 hours. Care must be taken that the resorcinol formaldehyde resin has a pH of 7.5 or above to avoid coagulation of the latices. If the pH of the resin is not 7.5 or above it may be adjusted by the addition of ammonium to the resin before it is added to the polybutadiene and vinylpyridene latices. A mixture of aqueous ammonium hydroxide is prepared by dissolving 7.2 pounds (3.3 kg.) of ammonium hydroxide in 9 gallons (34 L) of deionized water and after the resin latex mixture has been aged the aqueous ammonium hydroxide is added to the resin latex mixture in the main tank. The mixture is then agitated for a period of time to produce the adhesive system coating composition having a percent solid of 27 plus or minus 0.5, a pH of a 8.5 plus or minus 0.3, and a dip life of 50 hours. This adhesive system coating composition can be used to bind glass fibers to rubber matrices.

EXAMPLE V Preparation of Adhesive System Coating Composition Using Long-Chain, Thermoplastic, Water Soluble Resorcinol Formaldehyde Resin

To a mixing tank there was added 532 pounds (14.5 kg.) of polybutadiene latex, Goodyear 2374, and 400 pounds (181.4 kg.) of a styrene-butadienevinylpyridine latex, Goodyear 5622. In addition there was added 48 gallons (132 L) deionized water along with 8 pounds (3.6 kg.) of antioxidant, Bostex 294. In a separate tank 10 gallons (37.9 L) of deionized water was added along with 4 pounds (1.8 kg.) of antioxidant Paracure A-09 and 40 pounds (18 kg.) of a wax Mobilcer Q which was mixed for 10 minutes and then added to the main mixing tank containing the mixture of latices. After the long-chain, thermoplastic, water soluble resorcinol formaldehyde produced in Example III had been aged for 9 hours, it was slowly added to the main mixing tank that contained a mixture of latices and antioxidants and wax. After the resorcinol formaldehyde resin was added the mixture was aged for 10 hours. An aqueous solution of ammonium hydroxide was prepared by adding 2.4 pounds (0.18 kg.) of ammonium hydroxide to 4 gallons (15 L) of deionized water. This aqueous ammonium hydroxide solution was added very slowly to the resin latex mixture and was stirred for about 10 minutes. An aqueous resorcinol solution was then prepared by adding four pounds (1.8 kg.) of resorcinol to 4 gallons (15 L) of deionized water which was mixed together until the resorcinol was completely dissolved. The aqueous resorcinol solution was then added very slowly within about 15 minutes to the main mix tank containing a resin latex mixture. The mixture was then stirred for 25 minutes and then automatically agitated for one minute every half hour to produce an adhesive system coating composition having a percent solids of 27 plus or minus 0.5, a pH of 8.5 plus or minus 0.3, and a dip life of 50 hours. The resorcinol solution was added to the resin latex composition to improve the bonding characteristics of the adhesive system. The added resorcinol increases the adhesion level of the adhesion system by increasing the resin content and increase the plurality of the dip for better wettability and impregnation.

EXAMPLE VI The Preparation of a Long-Chain, Thermoplastic, Water Soluble Resorcinol Formaldehyde Resin and Adhesive System

To a pre-mixed tank there was added 24 gallons (91 L) of deionized water at 110° F. (43.4° C.). To the water in the reaction vessel, there was added 96 pounds (43.5 kg.) of resorcinol which was agitated until completely dissolved. To the aqueous solution of resorcinol there was added 56.8 pounds (25.8 kg.) of formaldehyde. The resorcinol and formaldehyde were reacted in the aqueous solution at a temperature of 78°-80° F. (26°-27° C.) at a pH of 5.0 plus or minus 0.5 for a period of time of 4 hours. An aqueous potassium hydroxide solution was prepared by dissolving 1.6 pounds (0.73 kg.) of potassium hydroxide in 40 pounds (18 kg.) of deionized water. At the end of the four hours reaction time of the resorcinol and formaldehyde under acidic conditions the aqueous solution of potassium hydroxide was added slowly to the reaction mixture. After the addition the pH was around 7.5 and the reaction was continued at a temperature of 78°-80° F. (26°-27° C.) for a period of 5 hours. At the end of this time the resorcinol formaldehyde resin produced was the long-chain, thermoplastic, water soluble resorcinol formaldehyde resin of the present invention.

In a main mix tank there was added 912 pounds (414 kg.) of a styrene-butadiene-latex Firestone SR6642, and 400 pounds (181.4 kg.) of a carboxy polybutadiene latex GenFlow® 8020 and 720 pounds of a polybutadiene styrene latex, Firestone S-272. To this main tank there was also added 140 gallons (530 L) of deionized water along with 16 pounds (7.26 Kg.) of antioxidant, Bostex 294. Then in a separate mix tank there was added 20 gallons (75.7 L) of deionized water and 8 pounds of an antioxidant Paracure A-09 along with 80 pounds (36.3 kg.) of wax, Mobilcer Q, which was mixed for 10 minutes, and then added to the main mix tank containing the mixture of latices. After the long-chain, termoplastic, water soluble, resorcinol formaldehyde resin produced above has aged for 9 hours it was slowly added to the main mixing tank containing the mixture of latices. After the resin was added the mixture was aged for 6 hours and 280 pounds (127 kg.) of Neoprene latex, Neoprene 735-A was added slowly to the mixture. An aqueous solution of ammonium hydroxide was prepared by dissolving 4.8 (2.2 kg.) pounds of ammonium hydroxide and 6 gallons (23 L) of deionized water. This aqueous solution of ammonium hydroxide was added to the resin latex mixture after the mixture had aged for about 30 minutes after the addition of Neoprene. The addition was accomplished very slowly and after the addition the mixture was aged for 15 minutes, and after 1 hour was placed on an agitator for automatic agitation of one minute each half hour to produce an adhesive systems coating composition having a solids content of 28.0 plus or minus 0.5, a pH of 8.5 plus or minus 0.3, a dip life of 60 hours.

EXAMPLE VII Coating Glass Fibers With Adhesive Systems Coating Composition Containing Long-Chain, Thermoplastic, Water Soluble, Resorcinol Formaldehyde Resin

Glass fibers that were formed at a fiber-forming bushing, sized with an aqueous sizing composition gathered into strand and wound onto a forming package that is then dryed and mounted on a creel are unwound and coated with the adhesive system coating composition of the present invention. Fiber glass strands such as G-75,5/0 or G-75,10/0 or G-75,15/0, which characteristically are 9.6×10⁻⁶ meters to 9.1×10⁻⁶ meters in diameter and have a filament count of 2,000 in a cord being constructed of 5 strands each strand having 400 filaments, are coated by the adhesive system coating composition of the present invention. Also, K fibers, such as, K-15 strand typically having 1,00 filaments therein each filament having a diameter of about 13.34 plus or minus 0.63 microns (5.25 plus or minus 0.25×10⁻⁴ inches) wherein 1 to 3 strands per cord are used, can also be coated by the adhesive system coating composition of the present invention. When G cord is to be used in bias belted tires the cord should be constructed to 5 strands and when the cord is to be used in radial tires, there should be 10 to 15 strands per cord.

The 10 to 15 strands cord allows higher packing of the cord per unit area, thereby providing greater strength to the tire carcass. This strength is necessary to obtain the desirable properties in radial ply tires. G fibers were sized with a chemical size containing predominantly polypropylene emulsion containing 25 percent by weight of polypropylene and 6 percent by weight of emulsifying agent and also containing smaller amounts of polyvinyl alcohol, and amide imidazolene, and methylacryloxypropyltrimethoxysilane. This sizing composition was applied to the fibers during formation and the strand formed therefrom was dried and/or cured in accordance with the method described in U.S. Pat. No. 3,655,353 herein incorporated by reference.

Adhesive system coating composition prepared in Example IV and Example V were used to coat the glass fiber cord. The glass fiber cord was prepared by coating 15 of the sized strands with the coating composition from Example IV and Example V. This cord was incorporated into a rubber stock and also used to reinforce the belts of pneumatic tires.

The tire cord properties of these coated fiber glass cords were tested for the adhesion level of the adhesive system in various rubber stocks. The results of these tests are presented below. The successful bonding of rubber to tire cord is measured by several tests one of these is strip adhesion. Strip adhesion for rubber coated glass cord is determined by the following method. A cylindrical drum is wrapped by a 10.2×26.7 centimeter×0.1 centimeters strip of rubber stock. The rubber stock occupied substantially all of the surface area of the cylindrical drum. The coated glass fiber yarn is wrapped about the rubber stock on the drum in a cylindrical fashion, providing a continuous layer of yarn over the rubber stock. The wound rubber stock has been moved from the cylinder and cut into a 7.6×25.4 centimeter sample. A strip of the 7.6×25.4 centimeter rubber is placed in a 7.6×25.4 centimeter mold and the above rubber strip with the coated strand thereon is placed in the mold with the strand side away from the first rubber strip. A number of 27.62×2.54 centimeter strips of Holland cloth are placed at opposite ends of the strand side of the rubber strip. Another 7.62×25.4 centimeter rubber strip is placed over the Holland cloth and lastly, a 7.62×25.4 centimeter rubber strip of coated strand thereon is placed on the last mentioned rubber strip with the strand side in contact with the last mentioned rubber strip. The mold is closed and the rubber cord laminate is cured at 4,780 pascals for 30 minutes at 149° C. The rubber cord laminate is removed from the mold and is allowed to simply cool overnight.

The laminate is cut into 14×2.54 centimeter strips and heated for 30 minutes at 121° C. after which the Holland cloth is removed from the laminate. After setting an Instron® test device for a gauge length of 1.27 to 1.9 centimeter and calibrating the unit for a cross head speed of 5.1 centimeter per minute, the bottom layer of the heated rubber and the exposed cord are placed in the top jaw, and the top layer of the heated rubber is placed in the bottom jaw of the test device. The Instron® test device is operated until a separation of 5.1 centimeter is obtained and the loading is noted. The top layer is inserted into the top jaw and the cord in the bottom jaw with a gauge length of 1.27 to 1.9 centimeters. The Instron® device is operated until a separation of 5.1 is obtained and the loading is noted. The test is repeated for the opposite end of the specimen and for additional specimens included in the example. The results of the test are averaged for adhesion of the cord to rubber.

The "In-rubber tensile" is determined by curing the cord in a rubber matrix and testing the glass fiber cord reinforced matrix in an Instron® device with a gauge of 17.8-19 centimeter and a cross head speed of 5.1 centimeter per minute. The jaws are separated and the force required to break the sample is recorded.

The results of the foregoing described test procedures are presented in Table I.

                  TABLE I                                                          ______________________________________                                                   Strip Adhesion in Various                                                      Rubber Stocks                                                                    Stock A.sup.1                                                                           Stock B.sup.2                                                                           Stock C.sup.3                                                lb./     lb./     lb./   In-Rubber-                                Cord        Rating*  Rating   Rating Tensile lb.                               ______________________________________                                         Coating     21/1.3   47/4.5   34/4.8 200                                       Composition of                                                                 Example IV                                                                     Coated with 41/4.7   45/5.0   44/5.0 210                                       Composition of                                                                 Example V                                                                      Coated with 36/4.8   49/5.0   47/5.0 229                                       Composition                                                                    Similar to                                                                     Example V                                                                      wherein the                                                                    Goodyear Latices                                                               are replaced by                                                                Firestone Latices                                                              (SR 6642 and                                                                   SR 272)                                                                        ______________________________________                                          *Rating 1-5:1 is adhesive failure, and 5 is cohesive failure                   .sup.1 Rubber Stock available from McCreary Tire & Rubber Co.                  .sup.2 Rubber Stock available from B. F. Goodrich Co.                          .sup.3 Rubber Stock available from Firestone Tire & Rubber Co.           

Tests were also performed on the fiber glass cord coated with the adhesive systems coating composition of the present invention, when the cord was bound to rubber and used in pneumatic tires. One such test is the Gristmill test which measures the compression fatigue resistance of the cord. A major part of the stress is applied to the outside shoulder of the tire where cord breakage is most likely to occur. Cord breaks in each tire belt are totaled and for uniformity, adjusted to breaks/meter of belt length.

The ambient gristmill test involves the following:

a. inflate tires to 24 psi at 75° F.,

b. mount one tire on the right front position of a standard vehicle which has been pre-loaded to 100 percent T and RA load at 24 psi. Record tire pressure at this point and do not make any adjustments,

c. Drive the vehicle at 15 miles per hour for 800 laps in counter-clockwise direction. Record temperature and pressure of tire at the end of the test.

d. X-ray the tested tire inflated to determine a condition of the cord.

The cold gristmill test involves

a. inflate tires at 24 psi (1.69 kg/km²) at 70° F. (21° C.).

b. tires are cooled for 4 hours to -40° F. (-40° C.) then one tire is removed from the cold box and placed on the right front position of the car. It is allowed to warm up to -25° F. (-32° C.) before starting the test. Record tire pressure at this point and do not make any adjustment,

c. drive the tire at 15 mph (8.05 km/hr) for ten laps in counter-clockwise direction. This constitutes one cold cycle. Record temperature and pressure of the tire at this point. Put tire back in the cold box for 4 hours at -40° C.

e. Repeat steps b, c, and d for the specified number of cycles.

f. X-ray the tested tire inflated to determine the cord breakage if any. The test conditions for both ambient and cold include an 85 foot (24.4 meters) diameter circle wherein 100 laps at 15 miles per hour in a clockwise direction are made at 100 laps at 15 miles per hour in (8.05 km/hr) counter-clockwise direction are made. The tires are inflated 24 psi (1.69 kg/cm²). The load is a T&RA rated load for 24 psi (1.69 kg/cm²) and the fixed position mounting is the front mounting. Table II presents the results of Gristmill Testing on the glass fiber yarn embedded in rubber stock with the use of the adhesive system of Examples IV, V, and VI, and a commercial glass radial tire cord.

                  TABLE II                                                         ______________________________________                                         Radial Tire Cord Performance                                                   Gristmill Test                                                                                            Cold Gristmill Test                                 Cord Coated                                                                               Ambient Gristmill Test                                                                         7 cycles:Breaks/                                    With:      1600 laps:Breaks/Meter*                                                                        Meter                                               ______________________________________                                         Example IV                                                                     Adhesive System                                                                           3               0                                                   Example V                                                                      Adhesive System                                                                           5               3                                                   Example VI                                                                     Adhesive System                                                                           15              100                                                 Commercial                                                                     Cord       10              4                                                   ______________________________________                                          *B/M is the average number of breaks per one meter of tire belt.         

In Table III Indoor Cold Wheel Test: 5° Slip angle involves cooling the tire to a -20° F.-290° C.) mounting tire on a loaded wheel and running for one hour. This is one cycle. This step is then repeated to a total of 4 cycles. The tire is stripped and the belts are rated. A rating of 7 is no cord failure and a rating of 1 is excessive cord breakage.

                  TABLE III                                                        ______________________________________                                         Radial Tire Cord Performance                                                   Indoor Cold Wheel Test:5° Slip Angle                                                      Belt Rating*                                                 Cord Coated With:                                                                           No. of Cycles                                                                             Top Belt  Bottom Belt                                  ______________________________________                                         Example IV                                                                     Adhesive System                                                                             4          4.5       6.8                                          Example V                                                                      Adhesive System                                                                             4          5.5       6.9                                          Commercial                                                                     Cord         4          5.5       6.5                                          ______________________________________                                          Belt Rating: 1 to 7: 1 is sever cord breakage and 7 is zero cord breakage                                                                               

The foregoing has described the composition of a long-chain, thermoplastic, water soluble phenolic aldehyde resin particularly a resorcinol resin which has improved flexibility along with toughness and the process for producing same. The foregoing has also described the use of the improved flexible tough phenolic aldehyde resin in an adhesive system coating composition, wherein the resin is combined with a latex or latices along with other conventional additives to produce a dip for fiberous material particularly glass fiber strand. The foregoing has also described the glass fiber cord produced with the use of the improved flexible and tough phenolic aldehyde resin present in an adhesive systems coating composition and the benefit of improved flexibility and improved resistance to compression fatigue of the glass fiber cord coated with the adhesive systems coating composition containing the improved flexible and tough phenolic resin. 

I claim:
 1. A method for preparing a thermoplastic, water soluble, resorcinol aldehyde resin with improved flexibility and toughness and having a major amount of trimer polymer with only a minor amount of dimer and higher oligomers and having slight cross-linking, comprising:a. reacting in the absence of methanol to less than 100 percent completion a resorcinol and an aldehyde in an amount of resorcinol to aldehyde in mole ratios in the range of 0.6 to about 2 at a pH in the range of about 3.5 to about 5.5 to limit formation of resorcinol alcohols for a period of time equivalent to the period of time in the range of about 1 hour to about 20 hours at a temperature in the range of about 30° F. (-1.1° C.) to about 122° F. (50° C.) to produce a resinous mixture containing predominantly trimer polymer with smaller amounts of dimer polymer and higher oligomer polymer along with unreacted resorcinol and unreacted aldehyde, and, b. continuing the reaction of the resorcinol and aldehyde and reaction mixture at a pH maintained in the range of above 7 to about 7.5 at a temperature in the range of about 50° F. (10° C.) to about 140° F. (60° C.) when the residence time is in the range of about 0.75 to about 20 hours to produce the flexible but tough resin mixture having a predominant amount of trimer polymer and having slight cross-linking.
 2. Method according to claim 1 wherein an acidic catalyst is added to the resorcinol compound and aldehyde in the first step.
 3. Method according to claim 1 wherein the pH is adjusted to above about 7 to about 7.5 by adding basic catalyst selected from the group comprising sodium, potassium or other alkali metal, and alkaline earth metal hydroxides and carbonates.
 4. Method according to claim 1 wherein the aldehyde is formaldehyde.
 5. In a method for preparing phenolic aldehyde resins by reacting the phenolic compound and an aldehyde at an acid pH and then at the alkaline pH, the IMPROVEMENT COMPRISING producing a resorcinol aldehyde resin with improved flexibility and toughness, and having a major amount of trimer polymer and only a minor amount of dimer and higher oligomers and having slight cross-linking, comprising:a. reacting in the absence of methanol to less than 100 percent completion resorcinol and aldehyde in an amount of resorcinol to aldehyde in the range of mole ratios of 0.6 to about 2 at a pH in the range of about 3.5 to about 5.5 to limit the formation of resorcinol alcohols for a period of time in the range of about 3 hours to about 10 hours at a temperature in the range of about 68° F. (20° C.) to about 95° F. (35° C.) to produce a resinous mixture containing predominantly trimer polymer with smaller amounts of dimer polymer and higher oligimer polymer along with unreacted resorcinol and unreacted aldehyde, and b. continuing the reaction of the resorcinol and aldehyde and reaction mixture at a pH in the range of above 7 to about 7.5 at a temperature in the range of about 68° F. (20° C.) to about 95° F. (35° C.), when the residence time is in the range of about 2.5 to about 10 hours to produce the flexible but tough resin mixture having a predominant amount of trimer polymer and having slight cross-linking. 